Process for breaking petroleum emulsions



Fatented Feb. 20, 1951 UNITED STATES "PATENT OFFICE PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, St. Louis, and Bernhard Kaiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd.,, Wilmington, Del., a corporation of Delaware No Drawing. Application December 10, 1948, Serial No. 64,462

19 Claims.

with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as Well as the application, of such chemical compounds, products, and the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our copehding application, Serial No. 64,463, filed Dec. 10, 1948.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in oil type that are commonly re- ,etc.-, and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanmt state throughout the oil I which constitutes the continuous phase of emulsion. I

j'It also provides an economical and rapid process .for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. and subsequent demulsification under the condithe tions just mentioned are of significant value in removing impurities, particularly inorganic salts,

from pipeline oil,

Demulsification as contemplated in the present application includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence otsucb precautionary measure. similarly. such Controlled emulsification demulsifier may be mixed with the hydrocarbon component.

Briefly stated, the present process is concerned with the breaking or resolving of petroleum emulsions by means of certain esters which are, in

turn, derivatives of specific synthetic products. These products are, in turn, the oxyalkylated. derivatives of certain resins hereinafter speci-i fled.

Thus, the present process is concerned with breaking petroleum emulsions of the water-1m oil type characterized by subjecting the emulsion to the action of the hydrophile resultant of the esterification reaction involving, on the one handg an acidic ester containing (a) at least one polyhydric alcohol radical; (b) at least one polybasic carboxylic acid radical; and (c) a plurality of acyloxy radicals, each having 8 to 22 carbon atoms derived from any detergent-forming monocarboxy acid having 8 to 22 carbon atoms, with the proviso that at least one of said acyloxy radicals is derived from hydroxylated detergentforming monocarboxy acid having 8 to 22 carbon atoms, each said polyhydric alcohol radical being ester-linked with a plurality of groups, each of i which groups contains at least one of said acyloxy radicals, the number of said groups esterlinked to eachpolyhydric alcohol radical being at least equal in number in each instance to the valency of the polyhydric alcohol radical, so that each polyhydric alcohol radical is free from any uncombined hydroxyl radical directly attached thereto and being additional to the number of such groups ester-linked to any other polyhyez. dric alcohol radical contained in the ester, and at least one of said groups containing a polybasic carboxylic acid radical, and on the other hand, i

certain hydrophile synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide, and (B) an oxyalkylation-sus- I ceptible, fusible, organic solvent-soluble, water'- insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over I 8 carbon atoms and reactive toward said phenol;

said resin being formed in the substantial abi sence of trifunctional phenols; said phenol being of the formula in which R. is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a'plurality ofdivalent radicals having the formula (RiOM, in.

which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals; and n is a numeral varying from 1 to with the proviso that at least 2 moles of alkylene oxide be intro-.

duced for each phenolic nucleus, and with the final proviso that the hydrophile properties of Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furtherymore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difficulties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensatiomand it and most of the higher aldehydes enter into self-resinification when treated with strong acids or alkalies.

7 On the other hand, higher aldehydes frequently beneficially afiect the solubility and fusibility of a resin. This is illustrated," for example, by the different characterissaid ester, as Well as said oxyalkylated resin, in

an equal weight of xylene are sufficient to produce an emulsion when said'xylene solution is shaken vigorously with one to three volumes of water.

For purpose of convenience what is said here-' inafter will be divided into four parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde;

Part 2 will be concerned with the oxyalkylation.

of the resin 50 as to convert it into a hydrophile hydroxylated derivative; Part 8 will be concerned with the preparation of the esters so as to yield the new composition or product which is particularly effective as a demulsifier; and Part4 will be concerned with the use of such esters as demulsifiers as hereinafter described. 7

PART 1 As to the preparation of the phenol-aldehyde resins reference is made to our co-pending applications, Serial 'l Tos. 8,730 and 8,731, both filed February 16, 1948 (both now abandoned). In such co-pending applications we described a fusible,

organic solvent-soluble, water-insoluble resin polymer of the formula R R n" R In such idealized representation 11. is a numeral varying from 1 to 13 or even more, provided that the resin is fusible and organic solventsoluble. R is a hydrocarbon radical having at least 4 and not over 8 carbon atoms. In the instant application R may have as many as 12 carbon atoms, as in the case of aresin obtained from a dodecylphenol.

oxides employed as reactants, then the aldehydes, and finally the phenols, for the reason that the latterrequire a more elaborate. description.

The alkylene oxides which may be used are.

the alpha-beta oxides having not more than 4 carbon atoms, to wit, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene Oxide, glycide and methylglycide...

' 'and quaternary ammonium bases. It is generally In the instant invention it may be first suitable to describe the alkylene tics of the resin prepared from para-tertiary amylphenol and formaldehyde on one hand, and

a comparable product prepared from the same phenolicreactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, Whereas the latter is soft and tacky, and'obviously easier to handle in the subsequent oxyalkylation procedure. I

iCyclic aldehydes'may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in additionto its aldehydic function, furfural can form vinyl condensationsby virtue of its unsaturated structure. The. production of resins from furfural for use in preparing reactants for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are 'acetaldehyde, propionic aldehyde, butyraldehyde, 2-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of ;glyoxal should be avoided due to the fact that it is tetrafunctional. However, our experience has been that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which .are used as intermediates in this invention are obtained with the use of acid catalysts or alkaline catalysts,.or without'the use of any catalyst at all. Among the I usefulalkaline catalyst are ammonia, amines,

accepted that when ammonia and amines are employed as catalysts theyenter into the con densation reaction and, in fact, may operate by initial combination'with the aldehydic reactant.

The compound ,hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difficult to present any f formula which would depict thestructure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between theuse of an. alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the prod- .ucts are-not identical where different basic mater'ialsareemployed. The basic materials employed imlude not only those previously enumerated but? also, the hydroxides. of the alkali metals, hYdIOXr. ides of the alkaline earth metals, salts of strong bases and weak acids such, as sodium acetate... etc.

Suitable phenolic, reactants include the following: Paraetertiarybutylphenol; para-secondarybutylphenol; para-tertiaryamy1phenol; paras econdary-amylphenol; para-tertiary-hexylphenol; para-isooctylphenol; ortho-phenylphenolj; para phenylphenol; ortho-benzylphenol; parabenzylphenol; and para-cyclohexylphenol, and" the. corresponding ortho-para substituted meta cresols and 3,5j-xylenolsr Similarly, one. may use. para,- or ortho-nonylphenol, or a mixtureyparaor ortho-decylphenol or a mixture, methylphenol; or paraor ortho-dodecylphenol.

For, convenience, the phenol has, previously been referred to as monocyclic in order to. differentiate from fused nucleus polycylic phenols, such, as substituted naphthols. Specifically, mono,

cyclic is limited to the nucleus, in which thehydroxyl radical, is attached. Broadly speaking,.

where a substituent is cylic, particularly aryl, obviously in the usual sense such, phenol is actually polycyclic although the phenolic hydroxy is not attached to a, fused polycyclic nucleus. Stated another way, phenols" in. which the hydroxyl group is directly attached tov a condensed or fused polycyclic, structure, are excluded. This matter, however, is clarified by the following consideration. The phenols herein contemplated for reaction may be. indicated by the following formula;

which R is selected from the class consisting ofhydrogen atoms and hydrocarbonradicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one 0c.- currence of R is the hydrocarbon subs-tituent and the other two occurrences are hydrogen atoms,

wise manner, beginning with the hydroxyl posi,---

tion as i one The manufacture of thermoplastic phenol-a1"- d'ehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted by a hydrocarbon group, and particularly by'one having at least- 4 carbon atoms and not more than 12 carbon. atoms, is well known. Ashas been previously pointed out, there is no objection to a methyl, radical provided it is present in. the 3 or 5 position.

Thermoplastic or fusible phenol-aldehyde resins are usually manufactured for the varnish trade andoil. solubility is of prime importance. For this reason, the common reactants employed are butylated phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that: employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difficulty, while when a water-insolubl phenol is employed. some. modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interracial area. Once the reaction starts to-a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. Sincecommercialforms of such acids are commonly their alkali salts, it is sometimes con- Venient to use a small quantity of such alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic su1fo-acids may be prepared in situ in the phenol employed, byreacting concentrated sulfuric acidwith a small proportion of the phenol. In such cases where Xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent. such as xylene is advantageous as hereinafter'described in detail. Another variation of procedure is-to employ such organic sulfo-acids, in the form of their salts, in connection with an alkaliecatalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenolis employed, an excess of an aldehyde, for instance. formaldehyde, may be employed without: two: marked a change in conditions of reaction and. ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and wasted. For all'pra'ctical purposes the molar ratio. of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or' sufficient; at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant' can be distilled off and thus recovered from the reaction mass. This same procedure may-be used; with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularl formaldehyde, may be increased over the. simple'stoichiometri'c ratio Qf ash-ea;

one-to-one or thereabouts. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much astwo moles offormaldehyde, for example, per mole of phenol, Or even more, with the result that only a small part of such aldehyde remains uncombined or is subsequently liberated during resinification. Structures which] have been advanced to explain such increased use of aldehydes are the following: OH OH O-H2C CH2OCH Such structures may lead to the production of;

cyclic polymers instead of linear polymers.-- For this reason, it has been previously pointed out that, although linear polymers have'by far the most important significance, the presentinvention does not exclude resins of such cyclic structures.

Sometimes conventional resinification procedure is employed using either acid or alkaline :catalysts to produce low-stage resins. may be employed as such, or may be altered. or

converted into high-stage resins, or in any event, into resins of higher molecular weight, by heating along with the employment of vacuum so as to split off water or formaldehyde, or both; Gfenerally speaking, temperatures employed, 'particu larly with vacuum, may be in the neighborhood of 175 to 250 C., or thereabouts.

It may be well to point out, however, that the Such resinsployed to mean a stage having 6 or 7 units or evenless; .In the appended claims we have used flow-stage to mean3 to 7 units based on aver-' age molecular weight.

The molecular weight .determinations, of course, require that the product be completely soluble in the particular solvent selected as, for instance, benzene. The molecular Weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less conveniently'perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of'Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suit- 7 able method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method'for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947).

Subsequent examples will illustrate the use of an. acid catalyst, an alkaline catalyst, and no catalyst. As far asresin manufacture per se is concerned, we prefer to use an acid catalyst,

and particularly a mixture of an organic sulfoacid and a mineral acid, along with a suitable solvent, 5 1. 1 as xylene, as hereinafter illustrated,

. in detail. -However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in different stages of 'resinification'. Resins so obtained are i also perfectly satisfactory.

amount of formaldehyde used may and does usually affect the length of the resin chain. Increasing the amount of the aldehyde, such as formal-I. size or molecular dehyde, usually increases the Weight of the polymer.

In the hereto appended claims there is'specified,i

among other things, the resin polymer'containing at least 3 phenolic nuclei. Such minimummolecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resin. As as matter of fact, using the procedures herein described or any conventional resinification procedure will yield products usually having definitely in excess of 3 nuclei. In other'words,

the average size of the resin is apt to be distinctly over the above values, for example, it may average. 7 to 15 units. Sometimes the expression flowstage"resin or low-stage intermediate is em In numerous instances the higher molecular weight resins, i. e., those referred to as high-stage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymir, yet it is almost certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual man-" her and having a molecular weight indicating the" presence of approximately 4 phenolic units or thereabouts may be subjected to such treatment, with the result that one obtains'a resin having approximately double this molecular weight.

The usual procedure is to use a secondary step,"

heating'the resin in the presence or absence of an inert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinification employing phenols of the kind here described, thereis little or no tendency to form binuclear compounds, i. e., dimers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde,

particularly where the substituent has 4 or 5 carbon atoms. Where the number of carbon atoms in a substituent approximates the upper limit specified herein, there may be some tendency to dimerization. The usual procedure to obtain a dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydi 'phenyhmethanes.

Although any conventional procedure ordinarily employed may be used in the manufacture obtained from substituted phenols are not resins as that term is used herein.

js'olvent such as xylene.

assists or th herein contemplated resins, or, for that matter, such resins may bepurchasedinthe open market, we have found it particularly desirable to use the procedures described elsewhere herein, and employing a combination of an organic sulfo- "acid and a mineral acid as a catalyst, and xylene as a solvent. By Way of illustration, certain subsequent examples are included, but it is to be understood the herein described invention is not concerned with the resins per se or with any particular method of manufacture but is con-- cerned with the use of reactants obtained by the subsequent 'oxyalkylation thereof. The phenolaldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularlyoxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous phase. It can, for example, be carried out by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension. Since the melting points of the resins are often higher than desired in 'the initial stage of oxyethylation, we have 'found it advantageous to use a solution or suspension of thermoplastic resin in an inert Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is no objection to having a solvent present during the resinifying stage if, in addition to being inert towards the resin, it is also inert towards the reactants and also inert towards water. Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, :propyl benzene, mesitylene, decalin (decahydronaphthalene), tetralin (tetrahydronaphthalene) ;eth-ylene glycol diethylether, diethylene glycol @diethylether, and tetraethylene glycol dimethylether, or mixtures of one or more. Solvents such as dichloroethylether, or

dichloropropylether may be'employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowlycom' blue with the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weightdeterminations.

The use of such solvents is :a convenient expe dient in the manufacture of the thermoplastic resins, particularly since the solvent gives a more liquid reaction mass and thus prevents overheat e ing, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaotion and also water present as part-of the form'- aldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary product of commerce mntaining about 37 /2 to 40% formaldehyde; is l the preferred reactant. When such solvent is used it is advantageously added at the beginning s t have a resinwhich can be handled more conveniently in "the oxyalkylation stage. If a more expensive s0lven't, such as decalin, is "elm 'ploye'ti,"xylene or other inexpensive solvent may be jidiiedhftf'the removal of decalin, if desired.

Imprepafihg resins from difunctional phenols itis common toemploy reactants of technical graxle. The substituted phenols herein contemplated 'areusua'llyderived from hydroxybenzene. As a rule, such substituted phenols are comparativ'ely free from unsubstituted phenol. We have generallyfound that the amount present is considerably less than 1% and not infreuuently in the neighborhood of 1 of 1%. or even less. The amount ofthe usual trifunctional phenol, such as hydro'xybenvene for metacresol, which can be tolerated is determined by the fact that actual cross-"l nking, if it takes place even in requently, "must not besufficientto cause insolubility at the completion ofkt'he 'resinincation stage or the lack d'fhyfircphile roperties at the com letion or the oxyalkylation stage.

The exclus on of such trifunctional phenols as hviiroxyben ene or metacre ol is not based on the fact that the more random or occa ional inclusion of 'an unsubstituted 'nhen l nu leu n the resin molecule 'or in one of several mol cules, foiexample. 'mark'edlv aiters the chara ter stics or the cxylkviateu d rivative. The pre ence of a phenyl radical having a reactive hv rogen atom able or having a'hydroxymthylol or a sub-.- st ut''d hydroxymethylol roup present is a no tentiet'l source of cross-l nking either during res;

1- i nificat ion or oxyalkylatio'n. Cross-linkingleads either to insoluble resins or to non-hydrop'hilic products resulting from the oxyalkylation procedure. With this rationale understood, it is obvi-v one that trif-unctional phenols are tolerable only "in a rhinorproportion and should not be present to the extent that insolubil ty is roduced in the resins, or that 'the product resulting from oxyalkylat on is gelatinous, robbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in dl-fier entiating between resoles, Novolaks, and resins ol'ota ner'il solely from difunctional phenols.

v ,Previous reference has been made to the fact thatlffusible or anic solvent-soluble resins are usuaiiv l near but may be cyclic. Such more complicated structure may be formed, particularly if .a resin prepared in the usual manner is converted into a higher stage resin b heat treat mer t in vacuum as; previously mentioned. lhis again is a reason 'foravoiding anv opportunity for-cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words. the presence of sw-h reactant may cause cross-linking in a con entional resiniflcation procedure. or in the oxvalkvlation pro edure, or in theheatand va uum tr at nt if it is em loyed as part of re in manufa ture.

Ourroutine procedure in examining a phenol ior suitabil t 'for preparin intermediates to be used in practicing the in ention is to prepare a resin emnloving formaldehyde in excess (1.2 moles of formaldehyde per mole of phenol) and using an acid catalyst in the manner described Example, 111 of our Patent 2,499,370 granted March "Z, 1950. It the resin so obtained is solventsoluble in any one-of the aromatic or other 501- vents previously referred to, it is then subjected to oxyethylation. During oxyethylation a temperature is employed of approximately to C. with addition of at least 2 and advanta- 11' geously up to 5.;moles of ethylene .pxide. per ,phe; polio hydroxyl. The oxyethylationj is'advantag fgeously conducted so as to requirefronl'a few minutes up to 5 to 10 hours.'. If the productso btained is Solvent-Soluble and self-dispersing 0.r :mulsifiable, or has emulsifying properties, the phenol is perfectly satisfactory from the standpoint of trifunctional phenol content. .The. soly'entmay be removed prior to the, dispersibility' :oremulsifiability test. When a productbecomes ,r'ubbery during oxyalkylation due to the presence :of, a small amount of trireactive phenol,v as prey io'usly mentioned, or for some other. reason, it 'ni-ay become extremely insoluble, and he longer lqualifies as being hydrophile asherein specified. increasin thesize of the aldehydicnucleus, for instance using heptaldehydeinstead of formalderlfiydeincreases,tolerance for trifunctional phenol f,. ..-'.Th,e presence of a trifunctional or tetrafunc ,tional phenol (such .as resorcinol .or. bisphenolA) 1% apt to produce de ectable-cross linkingarmin 's'olubilization but will not necessarily ,doso, especially if the proportion is small. .Resinification, involvi g difuncti a ph n ls. on ma lso produce. insolubilization, although. this. seems to be. a a m v d ctio l.o Wh tjis some m s a d in re a d t ,r si i cation. magi ,t ions, involving difunctional phenols only, This is presumably due to cross-linking- This appe ars to be contradictory to wh t. one. might expect in light of the theory of functionality in re'sini; ligation, It is true that under ordinary circume stances, or rather under the circumstancesgof bpnventional resin manufacture the procedures employing ,difunctional phenols are 'very apt to,

and almost invariably do, yield solvent soluble', fusible resins. However, when conventional proee'glures. are employed in connection with resins fer varnish manufacture or the like, there is involved the matter of color, ,solubili ty in..oil, 'et a When resins of the sameltype. are manu: tured, for the herein contemplated purpose, i. as a raw material to be: subje cted.to oxyal tion, such criteria of selection are .nelonger Psi ih h more drastic conditionsof resinification than thes ordinarily employed, to produce resins for the present purposes. Such more drastic ,condi: tions of resinification may include increased t l t of c lyst, hi hertemperatures,longer ti e)? reaction, s ent: r a ion i vbl ine Stated another way, on m use neat lalone or in combinationwith vacuum, etc.

e ot 9 i t on y. qq ee fhed with the fication react ons which yield the bulklpf a a t cu a y with, t em nor reacti ns 92 .q ih r in ma fac ure whi ha edf 1m.- eriahh in the re t n e ti n lfohthe ea' n t they Occur hh e mo e d ast qc nd h f hen rl t c a t T e in esti a limited much of their Work: to reactions involv- :ing phenols having two ,or less reactive hydrogen .Mhvh f h t a pee h t e most r h' o fuh'cfi ha l enol b t Z9 r hhv ors ve thhsse ?arsw cent and .most .up-to-dateinvestigations is per; '"tinent to the present invention insofar that much pf it is referring'to resinification involving difunctional phenols.

. For themoment, it may be simpler to consider a most typical type of fusible resin and forget for the time that such resin, at least under certain circumstances, is susceptible to further complications. Subsequently in the text it will be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type resins. This point is made for the reason that insolubles must be avoided in order to obtain the products herein contemplated for use as reactants.

The typical type of fusible resin obtained from a-para-blocked or ortho-blocked phenol is clearly differentiated from the Novolak type or resole type Ofresin. Unlike the resole type, such ,typical typepara-blocked or ortho-blocked phenol resini'rnay be heated indefinitely without passing into an infusible stage, and in this respect is similar to a l Tovolak. Unlike the Novolak type the addition ofa further reactant, for instance, more aldehyde, does not ordinarily alter iusibility of the difunctional phenol-aldehyde type resinj but such addition to a Novolak causes cross-linking by virtue of the available third functional position.

, heat-hardenableTesins, at least under certain where heat alone, or heat and vacuum, are employed, or in the oxyalkylation procedure. In its simplest presentation the rationale of resinification involving formaldehyde, for example, and adifunctional phenol would not-be expected to form cross-links. However, cross-linking sometimes occurs and it may reach the objectionable stage. However, provided that the preparation of resins simply takes into cognizance the present knowledge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest difficulty in preparing a very large number of resins of various types and. from-various reactants, and by means of different catalysts by different pro: cedures, all of which are eminentl suitable for the herein described purpose. I I

Now returning. some thought that cross-Uni?- ing 'can take place, even when difunctional phenols are used exclusively, attention is directed to the following: Somewhere during the course of resin manufactur e there maybe a potential cross-linking combination formed but' actual cross-linking may not take place until the subsequent-stage is reached, i. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or explained in terms of a theory of flaws or Lockerstellenwhich is employed in ex:

phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolubles may be related to the aldehyde used and the ratio of aldehyde, particularly formaldehyde, insofar that a slight variation may, under circumstances not understandable, produce insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a slight increase in the proportion of formaldehyde mav lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the structure of these resins.

All that has been said previously herein as regards resinification has avoided the specific reference to activity of a methylene hydrogen atom. Actually there is 'a possibility that under some drastic conditions cross-linking may take pace through formaldehyde addition to the methylene bridge, or some other reaction involving a methyljene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily reactive, possibly at times methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not'to be taken as a criterion of rejection for use as a reactant. In other Words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more a dehyde may change its characteristics markedly in regard to both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contem plated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from dif-unctional phenols and some of the hi her aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at 110 to 165 C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

1 Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin fsidentified as one which can be heated repeated- =Iy and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it. is obvious that a resin to be suitable need only be sufficiently fusible to permit processing to produce our oxyalkylated products and,

not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speak.-

fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied 'tothe mechanical properties of aresln, are useful intermediates. The bulk of all fusible resins of the. k nd herein described are thermoplastic.

The fusible o;r thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydrophile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expre sion water-insoluble is used to point out this characteristic of'the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a, number of companies and can be purchased in the open market; in the second place, there are a wealth of examples of suitable resins described in the literature. The third procedure is to follow the directions of the present application.

The polyhydric reactants, i. e., the oxyalkylation-susceptible, water-insoluble, organic solvent-soluble, fusible, phenol-aldehyde resins derived from difunctional phenols, used as intermediates to produce the products used in accordance with the invention, are exemplified by Examples Nos. 1a through 103a of our Patent 2,499,370, granted March 7, 1950, and reference is made to that patent for examples of the myalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as herein specified, or a Single reactive aldehyde, or a single oxyalkylating agent, Obviously, mixtures of reactants may be employed, as for example a mixture of para-butylphenol and para-amylphenol, or a mixture of para-butylphenol and para-hexylphenol, or parabutylphenol and para-phenylphenol. It is extremely diflicult to depict the structure of a resin derived from a single phenol. When mixture of phenols are used, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldheyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, one might be producin simultaneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the oxyalkylated derivatives of such resins, derived from such plurality of reactants, instead of being limited to a single reactant from each of the thre classes, is contemplated and here included for the reason that they are obvious variants.

PART 2 Havin obtained a suitable resin of the kind described, such resin is subjected to treatment with a low' molal reactive alpha-beta olefin oxide The olefin oxides employed are characterized by the fact that they contain not were carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide. Glycide may be, of course-considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides, The solubilizing elTect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygencarbon ratio. 1

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable -to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1:3, and in butylene. oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules. have been attached to the resin molecule, oxyalkylation may be satisfactorily c tinued using the more favorable members of the class, to produce the desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more 'efiective than propylene oxide, and propylene oxide is more effective than butylene oxide. Hydro'xy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide' (methyl glycide) is more eifective than b-utylene oxide. Since ethylene oxide isthe cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content; Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

which the initial reactants used in the practice of the present invention are prepared is advanta geously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. 1 The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i. e., irom zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups. r f

. It may be necessary to allow for the acidit of a resinin determining the amount of alkaline catalyst to be added in oxyalkylation, For'in stance, if a nonvolatile strong acid such as sul-.

furic acid is used to catalyze the resinification reaction, presumably after being convertedinto a sulfonic acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

."Itr is advantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and maybe permitted to be present in the final product used asa demulsifier, it is. our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is'used. Under such circumstances it may be necessary at times to use substantial pressures to obtain'efiective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required. I

However, even in the instance of high-melting resins, a solvent suchas xylene can be eliminated in either one of' two ways: After the introduction of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point. of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively. soft and solvent-free, can be reacted further in the usualmanner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Another suitable procedure is to use propylene oxide'or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethyl ene oxide, for instance, by dissolving the powdered resin in propylene oxide even though oxy-. alkylation i taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene oxide or butylene oxide, or a mixture which includes theoxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. Since ethylene oxide, is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner.

Attention is directed to the fact that the resins herein described must be fusible or soluble in anv organic solvent. Fusible resins invariably are soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to indicate or assure that the resin meets this requirement need not be the one used an insoluble solvent.

17 in oxya k nnd e solvent w ic a e 2s ceptible to oxyalkylation .are included in this group of organic solvents. Examples of such sol vents are alcohols and alcohol eth'ers. However, where a resin is soluble in an organic solvent, there are usually available other organic "sole vents which are not susceptible 1 oa y a f n, useful for the oxyalkylai -ion step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100 to 260 mesh, and a slurry or suspension prepared in xylene 0 1' the like, and subjected to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified possess reactive hy droxyl groups and are oxyalkylation susceptible.

' Considerable of what-is said immediately here.- matter is concerned with ability to Vary the hydrophile properties of the hydroxylated intermediate reactants from minimum hydrophile i properties to maximum hydrophile properties. Such properties in turn, of course, are effected subsequently by the acids employed for es teri- :iication and the quantitative nature of the ester ification itself, i. e., whetherit is total or p artial.

It may be well, however, to point out what has been said elsewherein regard to the hydroxylated intermediate reactants. See, for example, our co-pending applications, Serial Nos. 8,730

and 8,731, both filed February 16, 1948, and Se- 1 rial No. 42,133, filed August 2, 19,48, and Serial No. 42,134, filed August 2, 19.48 (all four cases now abandoned). The reason is that the esterification, depending on the acids selected, ,may

vary the hydrophile-hydrophobe balance inone direction or the other, and also invariably causes the development of some property which ,makes it inherently different from the two reactants from which the derivative ester is obtained.

Referring to the .hydrophile hydroxylatedin- .termediates, ,even more remarkable and equally difficult to explain, are the versatility andlthe utilityof these ,compounds considered as chemical reactantsas one goes from nini num hydro- ,nh e q r p rtyto ultimat max mum d p le property o i st c m n mum hyd qph pr e t ma .b d bed r h a th q n Where two ethyleneoxy radicals or moderatelyin n excess t reo a nt odu e he P enoli ydro y uc m m .h rophil p o r y or sub-surface-activity or minimum s urfac :eactivity means that the product shows at least emulsifying properties .orselfdispersion in cold oreven in warm distilled water (l5 to C.) in

.concentrations of 0.5% to 5.0%. These na terials are generally more soluble in cold water than warm water, and may even be very in- ,solub e in boiling water. Moderately hight'emperatures aid in reducing the viscosity of the solute under examination. Sometimes: if one continueszto shake a hot solution, even, though cloudy or containing an insoluble phase, one finds that solutiontakes place to giveahomo- ,geneous phase as the mixture cools. Suchselfdispersion tests are conducted in the absence of ,When the hydrophile-hydrophobe balance is above the indicated r inimum (2 rno es 'ofethylene oxide per nhenolic nuc eus or the couivalent) but insufficientto give a sol as described present 19% to of an inert solvent such as xylene. 'All that one need to do is to have a xylene solution within the range of 50 to parts by weight of oxyalkyiated derivatives and 50 to 10 partsby weight of xylene and mix such solution'with on e,'two or three times its volume of distilled'water and shake vigorously so as to obtain an emulsion which may be of the oil-inwater type or the water-in-oil type (usually the former) but, in any event, is clue to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solve'nt and' employ any more elaborate tests, if the solubility is not suflicient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, with adit'tle acetone added if reguired, making a rather concentrated solution, for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equiva lent solution to give the" previously suggested 9.5% to 5.0% strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is .a liquid or a liquid solution self-emulsifiable), such sol or dispersion is referred to asat least semi-stable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if theyremain atleast for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature 22 CI). Needless t0 say, atest can be made in presence of an insoluble solvent such as 5% to ;15% of xylene, as notedin previous examples. If such mixture, i. e., containing a water-insoluble solvent, is at least semi-stable, obviously the solvent free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements herei nafter described. One outstanding characteristic :property indicating surface-activity in a material isthe abiity to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when ,in the higher oxyalk yiated staga andYto form an emulsion in the lower and interniediatestag'es of oxyalkylation.

Allowancemust be made for the presence of a solvent in ;the final product in relation to the :hydrophile properties .of the final product. The principle involved 'in"th'.e' 'manufacture of the herein contemplated compounds for use as j'polyhydric reactants, isbased'on the conversion of :a hydrophob or no'ii h'ydrophile compound or m xture of"compounds"into'products which are distinctly hydrophi atleajstltofthe extent that they have emulsifying properties .or are self-emulsifyin '.t at is. when. "s a en. with wat r theyproduce stable or semi-stablesuspensions, for: in the presence of a water-insoluble solv nt. such as xy ene, an emu sion. In ldemu sifi ation, itfiis sometimes preferable to use a product having markedly enhanced hydro- :phi e ropert es over, and jabove the initial stage of self-emulsifiability, although we have found l tbat with. products of thetype used herein, most efficacious resu ts are obtain d with products which do not have hydrop'bi e properties beyond. the stage of self dispersibility;

' MTo e highl oxval yla ted resins give colloidal scluti ons pr sols which show typical prgpe'rtles 19 comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against parafiin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably-determined in this same manner but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surfaceactive emulsifying agents such as mahogany soap may produce a water-'in-oil emulsion or an oilin-Water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure'is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The. amount of xylene is invariably sufiicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-inwater type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serveto illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpOSe of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surfaceactive characteristics in the polyhydric reactants used in accordance with this invention.'

They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activienate 7 son, if it is desirable to determine the approxi mate point where selfeemulsification begins,

, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene suchproperties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2'moles per phenolic nucleus, for producing products useful for ty) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reathe practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is Well known that the size and nature or structure of the resin polymer obtained varies somewhat with theconditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of asecondary heating step, contain 3 to 6 or '7 phenolic nuclei with approximately 4%; or 5 nuclei as an average. More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinificatiori is a conventional procedure and may be employed if desired. Molecular weight, of course, ismeasured by any suitable procedure, particularly by cryoscopic methods;

but using the same reactants and using more drastic conditions of resinification one usually finds that higher molecular weights are indicated by higher melting points of the resins and a tendency to decreased solubility. See what has been said elsewhere herein inregard to a secondary step involving the heating of a resin with or without the use of vacuum.

We have previously pointed out that either an alkaline 0r acid catalyst is advantageously used in preparing the resin. A combination of catalysts is sometimes used in two stages; for instance, an alkaline catalyst is sometimes employed in a first stage, followed by neutralization and addition of a small amount of acid catalyst assua e employed in order 'to introduce -methylol groups in the intermediate stage. There is no indication that such groups appear in the final resin if prepared by the use of an acid catalyst. It is possible that such groups may appear in the finished resins prepared solely with an alkaline catalyst; but we have never been able to confirm this fact in an examination of a large number of resins prepared by ourselves. Our preference, however, is to use an acid-catalyzed resin, particularly employing a formaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have been able to determine, such resins are free from methylol groups. Asa matter of fact, it is probable th at in acid-catalyzed resinifications, the methylol structure may appear only momentarily at the very beginning of the reaction and in all probability is converted at once into a more complex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to prepare polyhydric reactants for use in the preparation of compounds employed in the present invention, is to determine the hydroxyl value by the Verley-Bolsing method or its equivalent. The resin as such, or in the form of a solution as described, is then treated with ethylene oxide in presence of 0.5% to 2% of sodium methylate as a catalyst in stepwise fashion. The conditions of reaction, as far as time or per cent are concerned, are within the range previously indicated. With suitable agitation the ethylene oxide, if added in molecular proportion, combines within a comparatively short time, for instance a few minutes to 2 to '6 hours, but in some instances requires as much as 8 to 24 hours. "A useful temperature range is from 125 to 225 C. The completion of the reaction of each addition of ethylene oxide in duction or elimination of pressure. An amount conveniently used for each addition is generally equivalent to amole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, a sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent as a rule varies from 70% by weight of the original resin to as much as five or six times the weight of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may 'give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that inth subsequent examples reference is made to the stepwise addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there pressures noted in the various examples or .else- Where.

It may be well to emphasize-the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at to C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and partcularly oxyethylation. What has been said previously is submitted primarily to emphasize the fact that these remarkab7e oxyalkylateol resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydric alcohols in a surface-active or sub-surface-active range without examining them by reaction with a number of the typical esters herein described and subsequently examining the resultant for utility, either in demulsification or in some other art or industry as referred to elsewhere, or as a reactant for the manufacture of more complicated derivatives. A few simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, us ng the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2 to 1; 6 to 1; 10 to 1; and 15 to 1. From a sampleof each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophle character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacity to form an emulsion when admixed with xyene or other insoluble solvent. If neither test shows the required minimum hydrophle property, repetition using 2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the- 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed in a comparatvely thin layer, for instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may require the use of increased amounts of alkylene oxide. However, if one does not even care to go to the trouble of calculating molecular weights, one can simply arbitrarilyprepare compounds containing ethylene oxide equivalent to about 50% to 15% by weight, for example 65% by weight, of the resin to be oxyethylated; a second example using approximately 200% to 300% by weight, and a third example using about 500% to 750% by weight, to explore the range of hydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be made by a very simple test using a pilot plant autoclave having a capacity of about to gallons as hereinafter described. Such laboratory-prepared routine compounds can then be tested for solubility and, generally speaking, this is all that is required to give a suitable variety covering the hydrophiie-hydrophobe range. All these tests, as stated, are intended to be routine tests and nothing more. They are intended to teach aperson, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly arbitrary manner, a series of compounds illustrating the hydrophile-hydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instance, oneshould know (a) the molecular size, indicating the number of phenolic units; (b) the nature of the aldehydic residue, which is usually CH2; and (c) the nature of the substituent, which is usually butyLamyl, or phenyl. With such information one is in substantially the same position as if one had personally made the resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units of the resin of the follow ,ing over-simplified formula:

H OH.

/ ''Examples '11) through 181), and the tables which appear in columns 51 through 56 of our said Patent2,4 99,3'70 illustrate oxyalkylation products from resins which are useful as intermediates for producing the esterified products used in accordance with the present application, such examples giving exact and complete details for carrying out the .oxyalkylation procedure.

The resins, prior to oxyalkylation, vary from tacky, viscous liquids to hard, high-melting s01- ids. Their color varies from a light yellow through amber, to a deep red or even almost black. In the manufacture of resins, particularly hard resins, as the reaction progresses the reaction mass frequently goes through a liquid state to a sub-resinousor semi-resinous state, often characterized by being tacky or sticky, to a final complete resin. As the resin is subjected to oxyalkylation these same physical changes tend to take place in reverse. If one starts with a solid resin, oxyalkylation tends to make it tacky or semi-resinous and further oxyalkylation makes the tackiness disappear and changes the product to a liquid. Thus, as the resin is oxyalkylated' it decreases in viscosity, that is, becomes more liquid or changes from a solid to a liquid, particularly when it is converted to the water-dispersible or water-soluble stage. The color of the oxyalkylated derivative is usually considerably lighter than'the original product from which it is made, varying from a pale straw color R R n R (n:1 to 13, or even more) is given approximately by the formula: (M01. wt. .of phenol -2) plus mol. wt. of methylene or substituted methylene radical. The molecular Weight of the resin would be n times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The righthand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resin molecular weight is given approximately by taking (n plus 2) times .the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculation will bein .error by several per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using .such an approximate weight, one need only introduce, for example, two molal weights of ethylene oxide or slightly more, per phenolic nucleus, to produce a product of minimal hydrophile character. Further oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large number of oxyeth ylated products of thetype described herein, we have found no instance where the use of less than 2 moles of ethylene oxidefperv phenolic nu- ...eleus gave desirable products. T

color.

to an amber or reddish amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick viscous sirup. Some products are waxy. The presence of a solvent, such as 15% xylene or the like, thins the viscosity considerablyand also reduces the color in dilution. No undue significance need be attached to the color for thereason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared as customarily employed in varnish resin manufacture, i. e., a procedure that excludes the presence of oxygen during the resinification and subsequent cooling of the resin, then of course the initial resin is much lighter in We have employed some resins which initially are almost water-white-and also yield a lighter colored final product.

Actually, in considering the ratio of alkylene oxide to add, and we have previously pointed out that this can be predetermined using laboratory tests, it is our actual preference from a practical standpoint to make tests on a small pilot plant scale. Our reason for so doing is that we make one run, and only one, and that we have a complete series which shows the progressive effect of introducing the oxyalkylating agent, for instance, the ethyleneoxy radicals. Our preferred procedure is as follows: We prepare a suitable resin,

-or for that matter, purchase it in the open marsuch resins are used, a solvent need not be added but may be added as a'matter of convenience or forcomparison, if, desired. We then add a catalyst, for instance, 2% of caustic soda, in the ass-1.99 8

form of a 20% to 30% solution, and remove the water of solution or formation. We then shut ofi the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have been added, equivalent to 7.50% of the original resin. We prefer a temperature of about 150 C. to 175" C. We also take samples at intermediate points as indicated in the following table:

oxyethylation to 750% can usually be completed within 30 hours and frequently more oruickly.

The samples taken are rather small, for instance, 2 to i ounces, so that no correction need be made in regard to the residual reaction mass. Each sample is divided in two. One-half the sample is placed in an evaporating dish on the steam bath overnight so as to eliminate the xylene. Then 1.5% solutions are prepared from both series of samples, i. e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be suificient to indicate hydrophile character or surface activity. i. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property. All these properties are related through adsorption at the interface, for example. a gasliquid interface or a liquid-liquid interface. If desired, surface activity can be measured in any one of the usual ways using a DuNouy tensiometer or dropping pipette, or any other procedure for measuring interfacial tension. Such tests are conventional and require no further description. Any compound having sub-surfaceactivity, and all derived from the same resin and oxyalkylated to a greater extent, i. e., those having a greater proportion of alkylene oxide, are useful as intermediates for the practice of this invention.

Another reason why we prefer to use a pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a laboratory scale test which will indicate whether or not a resin. although soluble in solvent, will yield an insoluble rubbery product, i. e., a product which is neither hydrophile nor surface-active, upon oxyethylation, "particularly extensive oxyethyl'ation. It is also obvious that one may have a solvent-soluble resin derived from a mixture of phenols having present 1% or 2% of a 'trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. .In other words, with resins from some such phenols, addition of 2 or 3 moles of the oxyalkylating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active intermediate which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable intermediate. It is obvious that this present procedure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its effect on solubility and also the fact that, if carried far enough, it causes incipient 'stringiness, then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced stringiness, or even the tendency toward a rubbery stage, is not objectionable so long as the final product is still hydrophile and at least sub-surface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like. and preferably an alcoholic solution is used. The point which we want to make here, however, is this: Stringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a difunctional phenol and an aldehyde produceanon-cross-linked resin molecule and if such molecule is oxvalkylated so as to introduce a plurality of hydroxyl groups in each molecule, then and in that event if subsequent etherification takes place, one is going to obtain cross-linking in the same general way that one would obtain cross-linking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However. sup ose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethyl ne oxide. This may be done in a com aratively short time, for instance, at or C. in 4 to 8 ho rs. or even less. On the other hand, if in an exploratory reaction. such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction reouired 4 or 5 times as long to introduce an equal amount of et ylene oxide employing the same temperature, then etherification might cause stringin ss or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyalkylat 'on as ra idly as pOSsible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermoplastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance. oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as 10% to 15% of xylene. Further oxyalkylation, particularly oxyethylation, may

different.

then yield a product which, insteadoffgiving' I HCH This fact, of course, presents no difiiculty for the reason that oxyalkylation can'be conducted .in each instancev stepwise, or ata gradual rate,

and samples taken at short intervals so as :to

arrive at a point where optimum surface activity.

or hydrophile character is obtained if desired; for products for use as intermediates in the practice of this invention, this is not necessaryand, infact, may be undesirable, i. e., reduce the efficiency of the product.

We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances, of course, such distribution can not be uniform for. the reason that we. have not specified that the molecules of ethylene oxide, for example, be added in multiples of the units pres ent in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum of two males of ethylene oxide per phenolicnucleus are added; this would mean an addition of 10 moles of ethylene oxide, but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, even assuming the most. uniform distribution possible, some of the polyethyleneoxy radicals would contain 3 ethylenoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce 25 moles ofethylene oxide there is no way to be certain that all chains of ethyleneoxy units would have 5 units; there might be some having, for example, 4 and 6 units, or for that matter 3 or 7 units. Nor is 'thereany basis for assuming that the number ofmolecules of the oxyalkylatfng agent added to each of the molecules of the resin is the same, or Thus, where formulae are g'ivenito genres 7 various organic solvents may 'be 'employed to verify that the'resin is organic solvent-soluble. Such solubility test merely characterizes the resin. The particular solvent used in such test may not be suitable for a molecularweight determination and, likewise, the solvent used in determining molecular weight may not be suitable as a solvent during oxyalkylation. For solution of the oxyalkylated compounds, or their derivatives a great variety of solvents may be employed, such as alcohols, ether alcohols, cresols, phenols, ketones, esters,,etc.,' alone or with the addition of water. Someof these are mentioned hereafter.

We prefer the use of benzene or diphenylamine as a solvent in making cryoscopic measurements.

The most satisfactory resins are those which are soluble in xylene or the like, rather than those which are soluble only in some other solvent con- ..taining elements other-than carbon and hydrogen, for instance, oxygen orchlorine. Such solvents are usually polar, semi-polar, or slightly polar in nature compared with xylene, cymene,

t u V V Reference to cryoscopicmeasurement is concernedwith the use-of benzene orother suitable ,compound as a solvent. Such method will show that conventional resins obtained, fcr 7 example, from para-tertiary amylphenol and formaldehyde in presence of an acid catalyst, will have a molecular Weight indicating '3, 4, 5 or somewhat greater number of structuralunits per molecule. If more drastic conditions of resinification are employed orif' such low-stage resinlis-subjected" to a vacuum distillation treatment as previously described, one'obtains a resin of a distinctly higher moleoularweight. Anymolecular weight determination used,'whether cryoscopic measurement or'otherwise, other than theconventicnal cryoscopic one employing benzene, should be checked soas toinsu're thatit gives consistent values on such conventional resins'as a control. Frequently all that is necessary to make an approximation illustrate or depict the oxyalkylated products; disr' tributions of radicals indicated are to be statisti:-

cally taken. Wehave, however,'included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any other oxyalkylating agent, to add.

In regard to solubility of the resins andjthe ployed. This limitation does not apply to solvents used in cryoscopic determinations for obvious of themolecular weight range is to'make acomparisonwith the dimer obtained by chemical combination of two'rnoles' of thesame phenol, and one mole of the same aldehyde under conditions to insure dimeriz'ation- 'As to the prepa- "ration of such dimers from substituted phenols, see Carswell, Phenoplasts, page 31. ,creased viscosity, resinous. character, and decreased solubility, etc, of the higher polymers in comparisonlwith the dimer, frequently are all The inth-at is required to establish that the resin contains-3 or more structural units per molecule.

ordinarily th'e' oxyalkylation is carried out in autoclaves providedjwith agitatorsorstirring de- 7 vices. *We' have found-that the speed of theagivsome cases; the change from slow speed agitation, -for example, in a laboratory autoclave agitation tation markedly influences the reaction time. In

with a stirrer operating at a speed of to 200 R. P. M., to high speed. agitation, with the stirrer operating'at 250 to 350 I reducesthe tim 29 required for oxyalkylation by about one-half to two-thirds. Frequently xylene-soluble products which give insoluble products by procedures employing comparatively slow speed agitation, give suitable hydrophile products when produced by similar procedure but with high speed agitation, as a result, we believe, of the reduction in the time required with consequent elimination or ourtailment of opportunity for curing or etherization. Even if the formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale operations, we have demonstrated that economical manufacturing results from continuous oxyalkylation, that is, an operation in which thealkylene oxide is continuouslyied to the reaction vessel, with high speed agitation, i. e., an agitator operating at 250 to 350 R. P. M. Continuous oxyalkylation, other condit ons being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more convenient for laboratory operation.

Previous reference has been made to the fact that in preparing esters or compounds of the kind herein described, particularly adapted for demulsification of water-in-oil emulsions, and for that matter for other purposes, one should make a complete exploration of the Wide varia tion in hydrophobe-hydrophile balance as previously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance of the oxyalkylated resins is imparted, as far as the range of variation goes, to a greater or lesser extent to the herein described derivatives. means that one employing the present invention should take the choice of the most suitable derivative selected from a number of representative compounds, thus, not only should a variety of resins be prepared exhibiting a variety of oxyalkylations, particularly oxyethylations, but also a variety of derivatives. This can be done conveniently in light of what has been said previously. From a practical standpoint, using pilot plant equipment, for instance, an autoclave having a capacity of approximately three to five gallons. We have made a single run by appropriat selections in which the molalratio of resin equivalent to ethylene oxide is one to one, 1 to 5, 1 to 10, 1 to 15, and 1 to 20. Furthermore, in making these particular runs we have used continuous addition of ethy ene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided that the pressure of the ethylene oxide was sufficiently great to pass into the autoclave, or else we have used an arrangement which, in essence, was the equivalent of an ethylene oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with the means for either Weighing the cylinder or measuring the ethylene oxide used volumetrically. Such procedure and arrangement for injecting liquids is, of course, conventional. The following data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five difi'erent variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that reaction is stopped or, obviously, if reaction is not started at the This beginning of the reaction period. Since the addition of ethylene oxide is invariably an exothermic reaction, whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, if any, (1)) amount of cooling water or other means required to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling water or equivalent, or if there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature which is usually the operating temperature. In other words, by experience we have found that if the initial reactants are raised to the indicated temperature and then if ethylene oxide is added slowly, this temperature is maintained by cooling water until the oxyethylation is complete. We have also indicated the maximum pressure that we obtained or the pressure range. Likewise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one period ends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has been subjected to further treatment. All this is apparent by examining the columns headed Starting mix, Mix at end of reaction, Mix which is removed for sample, and Mix which remains as next starter.

The resins employed are prepared in the manner described in Examples 1a through 103a. of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were prepared in 10 to 15-gallon electro-vapor heated synthetic resin pilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and completely described in their bulletin No. 2087 issued in 1947, with specific reference to Specification No. 71-3965.

For convenience, the following tables give the numbers of the examples of our said Patent 2,499,370 in which the preparation of identical resins on laboratory scale are described. It is understood that in the following examples, the change is one with respect to the size of the operation.

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by distilation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, /2 to one gallon, one can proceed through the entire molal stage of 1 to l, to 1 to 20, without remaking at any intermediate stage. This is illustrated by Example 104?). In other examples we found it desirable to take a larger sample, for instance, a 3-gallon sample, at an intermediate stage. As a result it was necessary in such instances to start with a new resin sample in order to prepare suflicient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been previously prepared were by-passed or ignored. This is illustrated in the tables where, obviously, it shows that the starting mix was not removed from a previous sample.

V Phenol for resin: Para-iertionfly amylgbhenol' Aldehyde for resin: Formaldehyde Date, June 22, 1948 l V [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 3a of Patent 2,499,370 but this batch designated 104a,]

Mix Which is Mix Which Re- Starting Mix gg figg of Removed for mains as Next Sample Starter Max Max Pressure Tem era- 1 52 Solubility Lbs. Lbs. Lbs Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. 801- Res- Sol- Res- Sol- Res- 3 801- Res- E156 vent in vent in vent in vent. in

First Stage Resin to EtO Molal Ratio 1:1. 14. 15. 75 0 14. 25 15. 75 4. 0 3. 3. 1. 0 10. 9 12. 1 3. 0 80 150 y; I Ex.No.104b I Second Stage Resin to EtO Molal Ratio l:5 l0. 9 12. 1 3. 0 10. 9 12. 1 '15. 25 3. 77 4. 17 5. 31 7. l3 7. 93 9. 94 158 Q ST Ex. No. 1055-.-

Third Stage Resin to EtO 7 Molal Ratio 1:10. 7 13 7. 93 9. 94 7.13 7. 93 19. 69 3. 29 3. 68 9. 04 3. 84 4. 25 10.65 60 173 $4; FS EX. N0. 106b. V 7 7 Fourth Stage Resin to EtO Mola] Ratio 1:15. 3. 84 4. 25 10. 65 3. 84 4. 25 16. 15 2. 04 2. 21 8. 55 1. 2. 04 7. 60 220 160 96 RS Ex. No. 107b e Fifth Stage Resin to EtO.- Molal Ratio 1:20. 1. 80 2. 04 7. 60 1. 80 2. 04 10. 2 150 M3 QS Ex. No. 108b I=Insoluble. ST=Slight tendency toward becoming soluble. FS=Fairly soluble. RS=Roadily soluble. QS=Quite soluble.

Phenol for resin: Nonylphenol Aldehyde for resin: Formaldehyde Date, June 18, 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 700 oi Patent 2,499,370 but this batch designated 10911.]

Mix Which is Mix Wbicb Re- Starting Mix g ggg Removed for mains as Next v Sample Starter Ma M x. ax. Time 7 7 Pressure Temp erahrs Solubility Lbs. Lbs. Lbs Lbs. Lbs. I b8 Lbs. Lbs. Lbs Lbs. Lbs. Lbs Sol- Res- 801- Res- E 801- Res- Sol- Resvent in vent in vent in vent in First Stage Resin to EtO. Molal Ratio l:1 15 0 15. 0 0 15.0 15. 0 3 5.0 5. 0 1. 0 l0. 0 l0. 0 2. 0 50 150 1% ST Ex. No. l09b.

Second Stage Resin to EtO. v Molal Ratio 1:5 10 10 2.0 10 10 9.4 2. 72 2.72 2.56 7. 27 7.27 6.86 100 147 2 D1 Ex. No. 110b v I Third Stage Resin to EtO. Molal Patio 1:10- 7. 27 7. 27 6.86 7. 27 7. 27 13. 7 4. 16 4.16 7. 63 3. 15 3. 15 '5. 95 1% S EX. No.11lb 7 Fourth Stage Resin to EtO Molal Ratio 1: i- 3. 15 3.15 5. 95 3. 15 3. 15 8. 95 1.05 1. 05 2. 95 2. 10 2.10 6.00 220 174 2% S Ex. No. l12b Fifth Stage Resin t0 EtO Molal Ratio 1:20- 2.10 2. 10 6. 00 2.10 2.10 8.00 220 183 VS Ex. No. 113b.

S Soluble. ST Slight tendency toward solubility. 7 Dl'. Definite tendency toward solubility. VS Very soluble.

Phenolifow nese'n': Pam octylphenvk Date, June 23, 24, 1948 [Resimmade-in piiotplamzsiwbaceh. approximately 25 pnundsgcamzsponding ta Sawfi Patent-($499,370 but thisbatcb designated-11411.]

I Mix Whiuhis 5 Mix WhichRe- Starting Mix fig g g' Removedfion E mainsasNext;

O Sample: Starter Max. Max. Time -Pressure- Tempsra- Solubility lbls. Ibs. Lbs gbls. .gbsi :Lbs 1152s. tn :lshblsi ,Ifibs'. z tulle esoes-z 0- S-= '0 vent in Eto vent in Eto vent in :vent i'n Eto First Stage Resin to EtOLH. MolaiERatl 1452 15.8 0 14.21 15.811 3.25. 3.1. 3.4 0.75 ?11.1. 312.4; 2.5;: 150. 1%? NS. Ex. No. 1141) Second Stage Resin to mam. MolaliRatlo 1: 112.1 12.4 r 2.5 11.1.: 12. 4 312.55 7.0; Z82i 7.881 4.1 i 4.58. 4.62 1001 17 1 54 SS. Ex. No. b

Third Stage Resin to EtOf MolaLRatio 1:10. 6.64 7.36= 0 6.64. 7.36151]. i 190 1% SI Ex. No. 116!) Fourth Stage Resin to 131505.... MOIBJJRfiCiO 1:15. 4.40 4.9 0 4.4. 4.9 14.8. 400- 160*. }5 VS. Ex. No. 1l7b.-

Fifth Stag;

Resin to EtOi. Mo1a1.Ratio1:20 4S1 4.58 4.62 4.1 4.58 18.52 260 172v 4, VB, Ex. N0. 1181);"...

S=So1uble. NS=Not soluble. SS nSomewhat'soluble. VS"=.Vax-y=s01nb1'e:

Phenul'for resz'nfi Me rnfitylphenat?v AZdeii.ydesfnr resin?" Formaldehyde Date, July 8-13, 1948 [Resin made pilotrplant size batch, approximately. 25 pounds, corresponding to 69a:ofrPatentr2,499,370 .butr this; batchrdesignated: 119a.)

i Mix Which is Mix Which-Re- Starting Mix fig fig Removezifor i mainsasgNext.

Sample; Starter Max M ax 7V PIQSSIHP 'Temp cra- Solubility Lbs. Ebs. libs; .Lbs. =Lbs. ,Lbs. Lbs. Lbsm. S01- Res- E8 801- Res- .g gg- .S'ol-L Res- Egg- :SloI-f Res.- ..g f vent in vent in :vent in :vent in First Stay;

Resin to Et0L-. MolallRatio 13565 16.35 0 13.65.16.353 3Z0: 9.551145 2.11: 4.1.1. 4.9 0.9 i 60 1% NS- Ex. N0. 11%.

Second Stage Resin to EtOI. MolallRatib 5.- 10. 12 1 0' 10 v12 10.75. 4.52.. 5.42 4.81 5.48; 6.58: 5:94. 140- 1912 S Ex..Nn'..120b

Third Stage Resin to E1101- Molal Ratib 1210. 5. 48 6. 58 f 5.94 5.48 6.58.10.85 90; 160 M S Ex. No. 1211) Fourth Stage Resin to EtOL 1 MolaLRatiO 1:15. 411 4.9 1 0.9 4.1 I 4.9, 13.15 i 171 1942 V3 Ex. No. 1225-.--

Fifth Stage 1 Resin to Et0i MnlaLRatie 1:20. 35.10 3.72 0.68 3.10.. 3.72.13.4& 320 17.0 94 VS: Ex. No. 1230...

S==Soluble. NS=Not soluble. VS=Very soluble.

Phenol for resin: Par(IL-secondary; b'utylphenbl 7 I Aldehyd'elfo'r 'resini Formaldehyde Date, July 14-15, 1948 V i [Resin made in pilot plant size batch, approximately 25 pounds, corresponding 1:021 01. Petent 2.499.370 but this batch designated 12411.1

Mix Which is Mix Which Re Starting Mix fig' figg of Removed for mains as Next g Sample Starter Max Max Time 7 Pressure Tempgerahm Solubility Lsbls. gm. Lbs Ibls. Ifibs. Lb; Lsbls. Ibs. Lbs Ibls. abs. Lbs o eso eso eso es- Y vent in Eto vent in Eto vent in Eto vent in E First Stage Resin to EtO v Molal Ratio 1 14.45 15.55 0 14.45 15.55 4. 5.97 6. 38 1.75 8.48 9.17 2.50' 150 M2 N5 Ex. No. 124b Second Stage Resin to EtO. V A g 7 Molal Ratio 1:5 8 48 9.17 2.50 8.48 9.17 16.0 5.83 -6.32 11.05 7 2.65 285 $4195 ('95 188 M; SB Ex. No. 125!) i Third Stage Resin to no..." Molal Ratio 1:10- 4. 82 5.18 0 4.82 5.18 14-25 400 183 3'5 7 S Ex. No. 12Gb Fourth Stage Resin to EtO v V Molal Ratio 1:15 3 4.15 0 3.85 4-15 17.0 120 180 36 VS Ex. No. 127b I Fifth Stage Resin t0 EtO v Molal Ratio 1:20- 2. 65 2.85 4. 2.65 2.85 15. 45 80 170 M2 VS Ex. No. 128b V S=Solub1e. NS=Not soluble. SS= Sdmewhe.fso1uble. SVS=Very soluble.

Phenol for resin: M enthyl Aldehgde'for resin: Prbpiorialdehyde.

Date, August 12-13, 1948 [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 8111 of Patent 2,499,370 but this batch designated 129a.]

; Mix Which is Miit Which Be- Starting Mix figg figg of Removed for mains as Next Sample Starter 7 M Time Pressu 'e Tem gerahm Solubility l'bls. Ifibs. Lbs lbls. libs. n5 IbIs. %bs. b Ibls. Ifibs. Lbs m! o eso eso eso esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to EtO I v V v Molal Ratio 121-- 12.8 17.2 12.8 17.2 2.75 4. 25 5.7 0.95 8.55 11.50 1'. 80 150 1 $6 Not soluble. EX. N0. 129b V Second Stage Resin to EtO 1 g j V Molal Ratio 1:5.. 8. 55 11. 50 1. 80 8. 55 11. 50 9. 3 4. 78 6. 42 5. 2 3. 77 '6. 08 '4'. 10 100 170 $6 Somewhat Ex. N0. b soluble.

Third Stage Resin to EtO 5 I Molal Ratio 1:10 3 77 5.08 4. 10 3. 77 5.08 13. 1 l T 100 182 H: Soluble. Ex. N0. 1310 1 Fourth Stage Resin to Et() 7 7 Molal Ratio 1:15. 5 2 7.0 5.2 7.0 17.0 3. 10 4.17 10.13 2.10 2.183 6.87' 200 182 V4 Verysoluble. Ex. No. 132!) g Fifth Stage Resin to EtO Molal Ratio 1:20 2 10 2.83 6.87 2.10 2.83 9. 19 "90 P16 Verysoluble. Ex. N 0. 1330-.---- V V V Phenol for resin: Para-tertiary amylphenol Date, August 27-31, 1948 [Resin made on pilot plant size batch, approximately pounds, corresponding to 42a of Patent 2,499,370 but this batch designated as 13411.]

Aldehyde for resin: Furfural Mix Which is Mix Which Re- Starting Mix fig ggg of Removed for mains as Next Sample Starter Max Max Pressuie Temp era- 13 Solubility gbls. gins. bs lribs. Lbs gbs. Lbs a s 1bs.sq.1n. tine, C.

0- cs- 0- es- 4 0- es- 0- esvent in Eto vent in vent in Eto vent in Eto First Stage Resin to E (0 MolaiRatlol 11.2 18.0 11.2 18.0 3.5 2.75' 4.4 0.85 8.45 13.6 2.65 120 135 $6 Not soluble... Ex. No. 134b Second Stage Resin to Eto MolalRatioi: 8.45 13.6 2.65 84513.6 12.65 5.03 8.12 7.55 3.42 5.48 5.10 150 M Somewhat Ex No. 13511 soluble.

Third Stage Resin to EtO Molal Ratio 1:10.- 4.5 8.0 4.5 8.0 14.5 2.45 4.35 7.99 2.05 3.65 6.60 180 163 Soluble. Ex. N0. 1361) Fourth Stage Re in to EtO- 'Molal Ratio 1:15-- 3.42 5.48 5.10 3.42 5.48 15.10 180 188 $6 Verysoluble. Ex. N0. 1376 Fifth Stage Resin to Et0. Molal Rati01:20 2.05 3.65 6.60 2.05 3.65 13.35 ,5 Verysoluble.

Ex. N 0. 138b Phenolfor resin: Mnthyl Aldehyde fo'r resin: Furfural Date. Sept. 23-24. 1948 [Resin made on pilot size batch, approximately 25 pounds, corresponding to 89a of Patent 2,499,370 but this batch designated as 13941.]

Mix Which is Mix Which Re- Starting Mix fig figg of Removed for mains as Next Sample Starter Max Pressuye 'Iempsragig Solubility Ibls. I bs. Lbs Ibls. abs. Lbs i b s. I bs. Lbs ghls. r bs. Lbs

O- 95- 0- 8S- 0- 88- 0- esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to Eton--- Molal Rati01:1 10.25 17.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 90 $6 Not soluble. Ex. No. 13%

Second Stage Resin to EtO--. Mole] Ratiolzia} 7.6 13.15 1.85 7.6 13.15 9.35 5.2 9.00 6.40 2.4 4.15 2.95 80 177 at Somewhat Ex. No. 1405..---. soluble.

Third Stage Resin to EtO "Mola1Rati01:10 4.22 6.98 4.22 6.98 10.0 9f 16' Soluble.

Ex. No. 1410 Fourth Stage Resin to EtO Mela] Rati01:15 3.76 6.24 3.76 6.24 13.25 100 171 $6 Verysohgblfi. Ex.No.142b

Filth Stage Resin to EtO Molal Ratio 1:20-. 2.4 4.15 2.95 2.4 4.15 11.7 90 150 k; Verysoluble; Ex. N0. 143b Phenol for re'sim'Para-octyl Aldehyde for-resin: 'Furfural' Date, October 7-8, 1948 Resin made on pilot plant size batch, approximately 25 pounds. corresponding to 42a of Patent 2,499,370 with 206 parts by weight of commercial para-octylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 144m] 1 r Mix Which is Q Mix Which Re- Starting Mix fig figg of Removed for mains as Next Sample Starter Max Ma:

- 4 Time p Pressure Temp erahm Solubility gbls. 115. Lbs ISJDIS. abs. Lbs lbls. abs. ge s. Ifibs. Lbs 9- o eso eso eso esvent in Eto vent in Eto vent in Eto vent 'in 1 First Stage Resin to 15130.... Mola1 Ratio 1:1 12. 1 18.6 12. 1 18.6 3. 0 5.38 8. 28 1. 34 6. 72 10. 32 1. 66 80 150 Insoluble.

Ex. No. 144b Second Stage Slight tend- Resin to EtO.-- ency to- Molal Ratio 1:5.- 9 14. 25 9. 25 14. 25 11.0 3. 73 5. 73 4.44 5. 52 .8. 52 6. 56 100 v177 942 Ward be- Ex. No. 1451)..." 7 coming soluble.

Third Stage Resin to EtO V Molal Ratio 1:10- 6.72 10.32 1.66 6.72 10.32 14.91 4. 97 7.62 11.01 1.75 2. 3.90 V 182 34 Fairly solu- Ex. N0. 14Gb"-.- ble.

Fourth Stage Resin to EtO.- Molal Ratio 1:15 5. 52 8. 52 6. 56 5. 52 8.52 1 9 81 p 100 176 M; Readily sol- Ex. No. l47b. r ubie.

Fifth Stage Resin to EtO-... .Molal Ratio 1:20- 1 75 2.70 3. 1.75 2.70 7 8 .4 k V, V V V 80 160 54' Quite solu- Ex. No. 148b.... V ble.

Phenol for resin: Para-phenyl .Aldehyde for resin: Furfural Date, October 11-13, 1948 [Resin made on pilot plant size batch. approximately 25 pounds, corresponding to 42a of Patent 2,499,370 with 170 parts by weight of commercial paraphenylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 14911.]

Mix Which is Mix Which Re- Starting Mix fig figg oi Removed for mains as Next 7 Sample Starter Max. Max. Time Pressuie Temp erahrs Solubility Ibls. 115. Lbs lbls. gbs. Lbs l b s. abs. Lbs Ibis. I bs. Lbs lbsascb P o eso eso eso es- Vent in Eto Vent in Eto vent in Eto vent in Eto First Stage Resin to EtO. .Molal Ratio 1: l3. 9 16. 7 13. 9 16. 7 3.0 "3. 50 4. 25 0. 80 10.35 I 12. 45 7 2. 20 j j )6 Insoluble.

Ex. NO. 149ba Second Stage Resin to EtO r ght tend- Molal Ratio 1. 1o. 35 12. 45 2. 20 10. 35 12. 45 12.20 5.15 6.19 6.06 5. 20 6.26 6.14 so 183 yi Ex No. 150b.. 1 r S0111- bllity.

Third Stage Resin to EtO. V Molal Ratio 1:10- 8 90 10.7 8.90 10. 70 19.0 5. 30 6.38 11.32 V 3.60 4. 32' 7. 68 V 90 '193 M2 Fairly solu- Ex. No. 15117"-.- ble.

Fourth Stage Resin to EtO. ,Molal Ratio 1:15- 5. 2C 6. 26 6.14 5.20 6. 26 V 16.6 V V V V V V 100 171 3'6 Readily sol- Ex. No. 152b uble.

Fifth Stage Resin to EtO I .Molal Ratio 1:20. 3. 6C 4.32 7.68 3. 60 4.32 1 5.68 Sample somewhatrubbery and gelat- 230 2 Ex. No. 1531;"--- inous but fairly soluble 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE HYDROPHILE RESULTANT OF THE ESTERIFICATION REACTION INVOLVING ON THE ONE HAND AN ACIDIC ESTER CONTAINING (A) AT LEAST ONE POLYHYDRIC ALCOHOL RADICAL; (B) AT LEAST ONE POLYBASIC CARBOXYLIC ACID RADICAL; AND (C) A PLURALITY OF ACYLOXY RADICALS EACH HAVING 8 TO 22 CARBON ATOMS DERIVED FROM ANY DETERGENT-FORMING MONOCARBOXY ACID HAVING 8 TO 22 CARBON ATOMS, WITH THE PROVISO THAT AT LEAST ONE OF SAID ACYLOXY RADICALS IS DERIVED FROM HYDROXYLATED DETERGENT-FORMING MONOCARBOXY ACID HAVING 8 TO 22 CARBON ATOMS, EACH SAID POLYHYDRIC ALCOHOL RADICAL BEING ESTERLINKED WITH A PLURALITY OF GROUPS, EACH OF WHICH GROUPS CONTAINS AT LEAST ONE OF SAID ACYLOX RADICALS, THE NUMBER OF SAID GROUPS ESTER-LINKED TO EACH POLYHYDRIC ALCOHOL RADICAL, SO THAT EACH EQUAL IN NUMBER IN EACH INSTANCE TO THE VALENCY OF THE POLYHYDRIC ALCOHOL RADICAL, SO THAT EACH POLYHYDRIC ALCOHOL RADICAL IS FREE FROM ANY UNCOMBINED HYDROXYL RADICAL DIRECTLY ATTACHED THERETO AND BEING ADDITIONAL TO THE NUMBER OF SUCH GROUPS ESTER-LINKED TO ANY OTHER POLYHYDRIC ALCOHOL RADICAL CONTAINED IN THE ESTER, AND AT LEAST ONE OF SAID GROUPS CONTAINING A POLYBASIC CARBOXYLIC ACID RADICAL; AND ON THE OTHER HAND CERTAIN HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 